JPH0269594A - Method for forming heavy hydrocarbon into more volatile component - Google Patents
Method for forming heavy hydrocarbon into more volatile componentInfo
- Publication number
- JPH0269594A JPH0269594A JP22079688A JP22079688A JPH0269594A JP H0269594 A JPH0269594 A JP H0269594A JP 22079688 A JP22079688 A JP 22079688A JP 22079688 A JP22079688 A JP 22079688A JP H0269594 A JPH0269594 A JP H0269594A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- hydrogenation
- treatment
- subjected
- heavy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 title abstract description 3
- 238000011282 treatment Methods 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000011973 solid acid Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 4
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 21
- 125000003118 aryl group Chemical group 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 10
- 239000003245 coal Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 239000004058 oil shale Substances 0.000 abstract description 4
- 239000000295 fuel oil Substances 0.000 abstract description 3
- 239000003027 oil sand Substances 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 238000007327 hydrogenolysis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は１石炭液化油などの重質炭化水素を原料として
水素化処理を行ない、より軽質なナフサなど軽質留分を
効率よく得る方法に関するものである。[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a method for efficiently obtaining lighter fractions such as naphtha by hydrotreating heavy hydrocarbons such as coal liquefied oil as a raw material. It is.
［従来技術及びその問題点〕
近年、エネルギー問題、特に化石燃料の枯渇化にともな
って重中質油などの炭化水素を原料とする水素化精製反
応に関する研究が精力的に行なわれている。特に、石炭
、オイルシェール、オイルサンドなどから得られる芳香
族環を多く含有する、重質油を効率よく軽質化すること
については、新燃料の用途拡大という見地からも、新し
い技術開発が強く望まれている。[Prior Art and its Problems] In recent years, with energy issues, especially with the depletion of fossil fuels, research has been actively conducted on hydrorefining reactions using hydrocarbons such as heavy and medium oil as raw materials. In particular, there is a strong need for the development of new technologies to efficiently lighten heavy oil, which contains many aromatic rings obtained from coal, oil shale, oil sands, etc., from the perspective of expanding the use of new fuels. It is rare.
このような軽質化技術としては、従来、水素化分解や、
接触分解（Ｆ（：Ｃ）が知られているが、芳香族留分が
多い重質炭化水素の軽質化反応は困難であることが知ら
れている。Conventionally, such lightening technologies include hydrocracking,
Although catalytic cracking (F(:C)) is known, it is known that it is difficult to lighten heavy hydrocarbons containing a large amount of aromatic fraction.
石炭液化プロセスなどで得られる芳香族成分が多い軽油
及び灯油留分は、セタン価あるいは煙点が低いため、そ
の用途開発にあたっては、芳香環の水素化を行なうこと
、あるいはこれを軽質化し、ガソリン留分を得ることが
好ましいと考えられる。Gas oil and kerosene fractions, which are rich in aromatic components and are obtained through coal liquefaction processes, have low cetane numbers or smoke points, so when developing their uses, it is necessary to hydrogenate the aromatic rings or to lighten them to make gasoline. It is considered preferable to obtain a fraction.
これらの留分の改質、精製反応を行い、芳香環の水素化
反応を行なったり、芳香環の開裂を伴う分解反応を行い
、ガソリンなどの軽質留分を得るためには水素化処理反
応を用いることが必要である。These fractions undergo reforming and purification reactions, hydrogenation reactions of aromatic rings, cracking reactions accompanied by cleavage of aromatic rings, and hydrogen treatment reactions to obtain light fractions such as gasoline. It is necessary to use
このためにアルミナ、ゼオライトなど酸性を有する固体
酸触媒の使用が有効であると考えられている。しかしな
がら、固体酸触媒をこれら留分の改質反応に直接利用し
た場合、これらの留分は多環芳香族および窒素含有化合
物に富むため、触媒反応が阻害されること、さらには、
触媒上への炭素質が急激に析出し、触媒活性が急速に低
下することが明らかにされている。そこで、水素化活性
の高い触媒を用い、芳香環の水素化および脱窒素等の水
素化精製反応を行ったり、さらには分解活性の高いゼオ
ライト系触媒を用いて水素化分解反応を行い、芳香環を
開裂させ、軽質化を行う２段水素化処理反応を用いるこ
とが有効と考えられる。For this purpose, it is considered effective to use a solid acid catalyst having acidity such as alumina or zeolite. However, when a solid acid catalyst is directly used for the reforming reaction of these fractions, the catalytic reaction is inhibited because these fractions are rich in polycyclic aromatics and nitrogen-containing compounds.
It has been revealed that carbonaceous substances rapidly precipitate on the catalyst and the catalyst activity rapidly decreases. Therefore, a catalyst with high hydrogenation activity is used to perform hydrorefining reactions such as hydrogenation and denitrification of aromatic rings, and a zeolite-based catalyst with high decomposition activity is used to perform a hydrogenolysis reaction. It is considered effective to use a two-stage hydrotreating reaction in which cleavage and lightening are performed.
一方、本発明者らの研究によれば、比較的重質な留分は
二段水素化処理によっても軽質化が困難であることがわ
かった。On the other hand, according to the research conducted by the present inventors, it has been found that it is difficult to lighten relatively heavy fractions even by two-stage hydrogenation treatment.
〔発明の課題〕
そこで１本発明は１重質炭化水素類を水素化処理により
、効率よく改質あるいは軽質化する方法を提供すること
をその課題とする。[Problems of the Invention] Therefore, an object of the present invention is to provide a method for efficiently reforming or lightening heavy hydrocarbons by hydrotreating them.
本発明者らは、前記課題を解決するために、種々研究を
重ねた結果１重質炭化水素類の水素化処理による効率的
な軽質化を妨げている原因としては、水素化反応過程お
よび第２段の水素化分解反応において、塩基性窒素含有
化合物などのへテロ化合物により触媒が容易に被毒され
ることにあると着想した。そこで１本発明者らは、あら
かじめ脱ヘテロ化合物処理を行った重質炭化水素を常法
により水素化精製処理した結果、効率よく水素化、脱窒
素反応が進むことがわかった。さらに、水素化処理後、
水素化活性金属を担持させた固体酸触媒の存在下で水素
化分解処理を行ったところ、重質炭化水素は効率よく軽
質化されることを見出し、本発明を完成するに至った。In order to solve the above-mentioned problems, the present inventors have conducted various studies and found that the reasons for preventing efficient lightening of heavy hydrocarbons by hydrotreating are the hydrogenation reaction process and the The idea was that the catalyst is easily poisoned by hetero compounds such as basic nitrogen-containing compounds in the two-stage hydrogenolysis reaction. Therefore, the present inventors have found that when heavy hydrocarbons that have been previously subjected to a deheterocompound treatment are hydrorefined using a conventional method, hydrogenation and denitrification reactions proceed efficiently. Furthermore, after hydrogenation treatment,
When hydrogenolysis treatment was carried out in the presence of a solid acid catalyst supporting a hydrogenation-active metal, it was discovered that heavy hydrocarbons were efficiently lightened, leading to the completion of the present invention.
即ち、本発明によれば、あらかじめ脱へテロ化合物処理
した重質炭化水素を水素化処理する軽質化方法及びあら
かじめ脱へテロ化合物処理した重質炭化水素を水素化精
製処理した後、水素化活性金属を担持した固体酸触媒の
存在下で水素化分解処理することを特徴とする重質炭化
水素の軽質化方法が提供される。That is, according to the present invention, there is provided a lightening method in which heavy hydrocarbons that have been previously treated to remove heterogeneous compounds are hydrotreated, and after the heavy hydrocarbons that have been previously treated to remove heterogeneous compounds are hydrorefined, the hydrogenation activity is A method for lightening heavy hydrocarbons is provided, which is characterized by carrying out a hydrocracking treatment in the presence of a solid acid catalyst supporting a metal.
本発明における重質炭化水素としては、沸点２５０℃以
上の成分を２０重量ｘ以上含むものが用いられる。この
ようなものとしては、石炭液化油、石油系重質油、オイ
ルサンド油、オイルシェール油等から得られた重質及び
軽質留分等がある。As the heavy hydrocarbon in the present invention, one containing 20 weight x or more of components having a boiling point of 250° C. or higher is used. These include heavy and light fractions obtained from coal liquefied oil, petroleum heavy oil, oil sand oil, oil shale oil, and the like.
本発明においては、先ず、重質炭化水素を脱ヘテロ化合
物処理する。この処理は、酸洗浄によって、あるいは酸
洗浄と塩基洗浄によって達成することができる。酸洗浄
は、硫酸や塩酸等の鉱酸を用いて行うことができる。ま
た、塩基洗浄は、水酸化ナトリウム、水酸化カリウム等
のアルカリを用いて行うことができる。これら酸洗浄や
塩基洗浄後には、水洗及び脱水を行って、水素化処理原
料としての重質炭化水素を得る。本発明では、脱へテロ
化合物処理により、重質炭化水素中の塩基性あるいは酸
性へテロ原子（窒素および酸素）の含量を重質換算で錦
以上、好ましくは２０％以上除去する。In the present invention, first, heavy hydrocarbons are subjected to a dehetero compound treatment. This treatment can be accomplished by acid washing or by acid washing and base washing. Acid cleaning can be performed using a mineral acid such as sulfuric acid or hydrochloric acid. Moreover, base washing can be performed using an alkali such as sodium hydroxide or potassium hydroxide. After these acid washings and base washings, water washing and dehydration are performed to obtain heavy hydrocarbons as raw materials for hydrogenation treatment. In the present invention, the content of basic or acidic heteroatoms (nitrogen and oxygen) in heavy hydrocarbons is removed by more than 20%, preferably 20% or more, in terms of weight, by the deheterocompound treatment.
本発明の第１段の水素化処理は、常法によって行うこと
ができる。例えば、アルミナ担体に、ニッケルとモリブ
デンあるいはコバルトとモリブデンを担持した触媒を用
い、反応温度：３５０〜４００℃、水素圧力＝１５〜２
０ＭＰａ、反応時間：１〜２ｈの条件下で水素化処理を
行う０本発明では、ＭＭＲにより測定された水素化精製
反応前後での芳香族炭素分率（ｆａ）を０．１以上、好
ましくは０．２以上減少させるように行う。The first stage hydrogenation treatment of the present invention can be carried out by a conventional method. For example, using a catalyst with nickel and molybdenum or cobalt and molybdenum supported on an alumina carrier, reaction temperature: 350-400°C, hydrogen pressure = 15-2
In the present invention, the aromatic carbon fraction (fa) before and after the hydrorefining reaction measured by MMR is 0.1 or more, preferably 0.1 or more. Do this to reduce the amount by 0.2 or more.
本発明の第２段の水素化分解処理は、水素化活性金属を
担持した固体酸触媒を用いて行う。固体酸としては、ゼ
オライトや、ゼオライトとアルミナとの混合物等が用い
られる。この場合、ゼオライトとしては、Ｙ型、モルデ
ナイト型、ＺＳＭ型等のものが用いられる。また、この
固体酸に担持させる金属としては、コバルト、モリブデ
ン、ニッケル、タングステン等があり、好ましくは、ニ
ッケルとモリブデンの組合せ、あるいはコバルトとモリ
ブデンの組合せが用いられる０反応条件としては、反応
温度：３００〜４４０℃、好ましくは４００〜４２５℃
、水素圧：３−２３−２Ｏ、好ましくは５＝１５ＭＰａ
、反応時間：２０〜２４０分、好ましくは６０〜１２０
分の条件が用いられる。The second-stage hydrocracking treatment of the present invention is carried out using a solid acid catalyst supporting a hydrogenation-active metal. As the solid acid, zeolite, a mixture of zeolite and alumina, etc. are used. In this case, the zeolite used is Y type, mordenite type, ZSM type, etc. The metal supported on this solid acid includes cobalt, molybdenum, nickel, tungsten, etc., and preferably a combination of nickel and molybdenum or a combination of cobalt and molybdenum is used.Reaction conditions include reaction temperature: 300-440°C, preferably 400-425°C
, hydrogen pressure: 3-23-2O, preferably 5=15MPa
, reaction time: 20-240 minutes, preferably 60-120 minutes
Conditions for minutes are used.
次に本発明を実施例によりさらに詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
原料油として、石炭液化油からの重質留分（５４８℃以
上の成分：２１重量対、窒素成分：０．６７重景気、酸
素成分＝２．３重量Ｘ）を用いた。As the raw material oil, a heavy fraction from coal liquefied oil (components at 548° C. or higher: 21 weight vs. nitrogen component: 0.67 heavy economy, oxygen component = 2.3 weight X) was used.
また、原料油として石炭液化油からの軽質留分（沸点２
００−３５０℃、窒素成分：０．３６重量２．酸素成分
：１．２重量％）を用いた。In addition, light distillates from coal liquefied oil (boiling point 2
00-350℃, nitrogen component: 0.36 weight 2. Oxygen component: 1.2% by weight) was used.
これらの原料油を用いて以下の処理を行った。The following treatments were performed using these raw material oils.
（脱ヘテロ化合物処理）
原料油１００ｇを、０．ＩＮ塩酸、０．ＩＮ水酸化ナト
リウム及び蒸留水の各々２００ｍＱ入った分液漏斗のそ
れぞれに入れ、１０分間激しく振とうした後、放置し、
水層と油層が分離するのを待ち、油層を分液゛した。(Dehetero compound treatment) 100g of raw oil was treated with 0. IN hydrochloric acid, 0. Pour into separate funnels containing 200 mQ each of IN sodium hydroxide and distilled water, shake vigorously for 10 minutes, and leave to stand.
After waiting for the water and oil layers to separate, the oil layer was separated.
この操作をいずれも３回繰返した。また、別に、原料油
を、前記の塩酸処理と水酸化ナトリウム処理とを組合せ
て処理した。このようにして処理された原料油をロータ
リーエバポレーター及び無水硫酸ナトリウムを用いて油
層中の水分を除去した。This operation was repeated three times. Separately, the raw material oil was treated by a combination of the above-mentioned hydrochloric acid treatment and sodium hydroxide treatment. The water in the oil layer of the raw oil thus treated was removed using a rotary evaporator and anhydrous sodium sulfate.
前記のようにして処理された原料油中の窒素含量を次表
に示す。The nitrogen content in the raw material oil treated as described above is shown in the following table.
表−１
（水素化処理）
前記のようにして得られた各試料油を、オートクレーブ
を用いて第１段の水素化精製処理を行った後、得られた
生成油を、オートクレーブを用いて第２段の水素化分解
処理を行った。これらの水素化処理の条件は次の通りで
あった。Table 1 (Hydrotreatment) After each sample oil obtained as described above was subjected to the first stage hydrorefining treatment using an autoclave, the obtained product oil was subjected to the first stage hydrorefining treatment using an autoclave. A two-stage hydrocracking treatment was performed. The conditions for these hydrogenation treatments were as follows.
（１）第１段水素化処理
〔触媒〕
アルミナ担体にＮｉ：２．３重量％及びＭｏ：１２重量
２を担持させた触媒
〔反応条件〕
反応温度：３７５℃
水素圧：１４．７ＭＰａ
反応時間：２時間
次に、第１段の水素化精製反応によって得られた生成油
の性状を表−２に示す。ｆａはＮＭＲ測定によって得ら
れた芳香族炭素分率を示しており１重質酸分および軽質
成分の出発原料のｆａ値はそれぞれ０．７９および０．
６１である。(1) First stage hydrogenation treatment [Catalyst] Catalyst in which Ni: 2.3% by weight and Mo: 12% by weight 2 are supported on an alumina carrier [Reaction conditions] Reaction temperature: 375°C Hydrogen pressure: 14.7MPa Reaction time : 2 hours Next, the properties of the produced oil obtained by the first stage hydrorefining reaction are shown in Table 2. fa indicates the aromatic carbon fraction obtained by NMR measurement, and the fa values of the starting materials for 1 heavy acid and light components are 0.79 and 0.79, respectively.
It is 61.
表−２
（２）第２段水素化処理
〔触媒〕
アルミナ担体にＮｉ：１．７重量％及びＭｏ：８．０重
量％を担持した触媒
〔反応条件〕
反応温度＝４２５℃
水素圧：１４．７ＭＰａ
反応時間：２時間
次に、前記第１段及び第２段の各水素化処理によって得
られたそれぞれの生成油の性状を次表に示す。Table 2 (2) Second stage hydrogenation treatment [Catalyst] Catalyst with Ni: 1.7% by weight and Mo: 8.0% by weight supported on an alumina carrier [Reaction conditions] Reaction temperature = 425°C Hydrogen pressure: 14 .7 MPa Reaction time: 2 hours Next, the properties of each product oil obtained by the first and second stage hydrogenation treatments are shown in the following table.
なお、軽質留分（試料油Ｎα１〜ＮＱ４）についての軽
質化率（Ｌ）は次式で表おされる。Note that the lightening rate (L) for the light fraction (sample oils Nα1 to NQ4) is expressed by the following formula.
Ａ：試料油中の沸点２００℃以上の成分の容−ｉ％８：
生成油中の沸点２００℃以上の成分の容ｉ％また１重質
留分（試料油Ｎα５〜Ｎα８）についての軽質化率（Ｈ
）は次式で表わされる。A: Volume of components with a boiling point of 200°C or higher in sample oil -i%8:
Volume i% of components with a boiling point of 200°C or higher in the produced oil and the lightening rate (H
) is expressed by the following formula.
Ｃ：試料油中の沸点５４８℃以上の成分の容量算り：生
成油中の沸点５４８℃以上の成分の容量Ｚ表−３
前記と同様に酸洗浄してペテロ化合物を除去し、次いで
、実施例１と同様にして、第１段及び第２段の水素化処
理を行った。その結果を表−４に示す。C: Calculation of the volume of components with a boiling point of 548 °C or higher in the sample oil: Volume of components with a boiling point of 548 °C or higher in the produced oil Z Table-3 The petro compound was removed by acid washing in the same manner as above, and then the The first and second stage hydrogenation treatments were carried out in the same manner as in Example 1. The results are shown in Table 4.
また、比較のために酸洗浄を施さないでそのまま２段の
水素化処理を行った結果もあわせて示す。For comparison, the results of two-stage hydrogenation treatment without acid washing are also shown.
表−４
実施例２
Ｍ科油としてオイルサンド油からの重質留分（窒素含量
：０．３８ｔｅｔぶ）、オイルシェール油からの重質留
分（窒素含量：０．９９ｗｔ％）及び石油からの重質留
分（窒素含量：０．１８ｗｔ％）をそれぞれ用いて、こ
れを〔発明の効果〕
以上から明らかな通り、本発明によれば、芳香族性に富
み、窒素化合物などのへテロ原子を多く含む重質炭化水
素類から、付加価値の高い芳香環が水素化された炭化水
素および軽質な炭化水素類を効率よく製造することがで
きる。Table 4 Example 2 Heavy fraction from oil sand oil (nitrogen content: 0.38 wt%), heavy fraction from oil shale oil (nitrogen content: 0.99 wt%) and petroleum oil as M family oil [Effects of the Invention] As is clear from the above, according to the present invention, the heavy fraction (nitrogen content: 0.18 wt%) of Hydrocarbons with hydrogenated aromatic rings and light hydrocarbons with high added value can be efficiently produced from heavy hydrocarbons containing many atoms.
即ち、本発明では脱へテロ化合物処理により触媒被毒成
分である塩基性化合物を除去することにより、水素化精
製反応で芳香環の水素化反応および脱窒素反応が進行し
、生成物の性状が改質される。また、脱ヘテロ化合物処
理、水素化反応に引続いて第２段の水素化分解反応を行
なえば軽質化反応を効率よく進行させることができる。That is, in the present invention, by removing basic compounds that are catalyst poisoning components through the dehetero compound treatment, the hydrogenation reaction and denitrification reaction of aromatic rings proceed in the hydrorefining reaction, and the properties of the product change. modified. Moreover, if the second stage hydrogenolysis reaction is performed subsequent to the deheterocompound treatment and the hydrogenation reaction, the lightening reaction can proceed efficiently.
特許出願人 工業技術院長 飯 塚 幸 三１１〜１削Patent applicant: Director of the Agency of Industrial Science and Technology Yuki Iizuka 311-1 cut
Claims (2)
を水素化処理することを特徴とする重質炭化水素の軽質
化方法。(1) A method for lightening heavy hydrocarbons, which comprises hydrotreating heavy hydrocarbons that have been previously treated to remove hetero compounds.
を水素化精製処理した後、水素化活性金属を担持した固
体酸触媒の存在下で水素化分解処理することを特徴とす
る重質炭化水素の軽質化方法。(2) A method for producing heavy hydrocarbons characterized by subjecting heavy hydrocarbons that have been previously treated to remove heterocompounds to hydrorefining treatment, and then subjecting them to hydrocracking treatment in the presence of a solid acid catalyst supporting a hydrogenation-active metal. Lightening method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22079688A JPH0269594A (en) | 1988-09-03 | 1988-09-03 | Method for forming heavy hydrocarbon into more volatile component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22079688A JPH0269594A (en) | 1988-09-03 | 1988-09-03 | Method for forming heavy hydrocarbon into more volatile component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0269594A true JPH0269594A (en) | 1990-03-08 |
| JPH0587111B2 JPH0587111B2 (en) | 1993-12-15 |
Family
ID=16756702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22079688A Granted JPH0269594A (en) | 1988-09-03 | 1988-09-03 | Method for forming heavy hydrocarbon into more volatile component |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0269594A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9067798B2 (en) * | 2009-08-07 | 2015-06-30 | Tokuyama Dental Corporation | Method for producing silica-zirconia composite particles each coated with silica layer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4849801A (en) * | 1971-10-27 | 1973-07-13 | ||
| JPS4938081A (en) * | 1972-08-25 | 1974-04-09 | ||
| JPS56122890A (en) * | 1980-02-01 | 1981-09-26 | Suntech | Method of raising quality of liquefied coal |
| JPS5759987A (en) * | 1980-09-29 | 1982-04-10 | Kobe Steel Ltd | Hydrogenation and liquefaction of brown coal |
-
1988
- 1988-09-03 JP JP22079688A patent/JPH0269594A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4849801A (en) * | 1971-10-27 | 1973-07-13 | ||
| JPS4938081A (en) * | 1972-08-25 | 1974-04-09 | ||
| JPS56122890A (en) * | 1980-02-01 | 1981-09-26 | Suntech | Method of raising quality of liquefied coal |
| JPS5759987A (en) * | 1980-09-29 | 1982-04-10 | Kobe Steel Ltd | Hydrogenation and liquefaction of brown coal |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9067798B2 (en) * | 2009-08-07 | 2015-06-30 | Tokuyama Dental Corporation | Method for producing silica-zirconia composite particles each coated with silica layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0587111B2 (en) | 1993-12-15 |
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